EMM-23 molecular sieve materials, its synthesis and use

ABSTRACT

A new molecular sieve material is designated as EMM-23 and has, in its as-calcined form, an X-ray diffraction pattern including the following peaks in Table 1: 
     
       
         
               
               
               
             
                 TABLE 1 
               
                   
               
                   
                 d-spacing (Å) 
                 Relative Intensity [100 × I/I(o)] 
               
                   
               
                   
                 17.5-16.3 
                 60-100 
               
                   
                 10.6-10.1 
                 5-50 
               
                   
                 9.99-9.56 
                 20-70  
               
                   
                 6.23-6.06 
                 1-10 
               
                   
                 5.84-5.69 
                 1-10 
               
                   
                 5.54-5.40 
                 1-10 
               
                   
                 4.29-4.21 
                 1-10 
               
                   
                 3.932-3.864 
                 1-10 
               
                   
                 3.766-3.704 
                 5-40 
               
                   
                 3.735-3.674 
                 1-10 
               
                   
                 3.657-3.598 
                 1-10 
               
                   
                 3.595-3.539 
                 1-20

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage Application of InternationalApplication No. PCT/US2012/047910 filed Jul. 24, 2012, which claims thebenefit of and priority to U.S. Patent Application No. 61/514,939 filedAug. 4, 2011, the disclosures of which are incorporated herein byreference in their entireties.

FIELD

This invention relates to a novel molecular sieve material, designatedas EMM-23, its synthesis, its use as an adsorbent, and a catalyst forhydrocarbon conversion reactions.

BACKGROUND

Molecular sieve materials, both natural and synthetic, have beendemonstrated in the past to be useful as adsorbents and to havecatalytic properties for various types of hydrocarbon conversionreactions. Certain molecular sieves, zeolites, AIPOs, mesoporousmaterials, are ordered, porous crystalline materials having a definitecrystalline structure as determined by X-ray diffraction (XRD). Withinthe crystalline molecular sieve material there are a large number ofcavities which may be interconnected by a number of channels or pores.These cavities and pores are uniform in size within a specific molecularsieve material. Because the dimensions of these pores are such as toaccept for adsorption molecules of certain dimensions while rejectingthose of larger dimensions, these materials have come to be known as“molecular sieves” and are utilized in a variety of industrialprocesses.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline silicates. Thesesilicates can be described as rigid three-dimensional framework of SiO₄and Periodic Table Group 13 element oxide (e.g., AlO₄). The tetrahedraare cross-linked by the sharing of oxygen atoms with the electrovalenceof the tetrahedra containing the Group 13 element (e.g., aluminum) beingbalanced by the inclusion in the crystal of a cation, for example aproton, an alkali metal or an alkaline earth metal cation. This can beexpressed wherein the ratio of the Group 13 element (e.g., aluminum) tothe number of various cations, such as H⁺, Ca²⁺/2, Sr²⁺/2, Na⁺, K⁺, orLi⁺, is equal to unity.

Molecular sieves that find application in catalysis include any of thenaturally occurring or synthetic crystalline molecular sieves. Examplesof these molecular sieves include large pore zeolites, intermediate poresize zeolites, and small pore zeolites. These zeolites and theirisotypes are described in “Atlas of Zeolite Framework Types”, eds. Ch.Baerlocher, L. B. McCusker, D. H. Olson, Elsevier, Sixth RevisedEdition, 2007, which is hereby incorporated by reference. A large porezeolite generally has a pore size of at least about 7 Å and includesLTL, VFI, MAZ, FAU, OFF, *BEA, and MOR framework type zeolites (IUPACCommission of Zeolite Nomenclature). Examples of large pore zeolitesinclude mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X,omega, and Beta. An intermediate pore size zeolite generally has a poresize from about 5 Å to less than about 7 Å and includes, for example,MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework typezeolites (IUPAC Commission of Zeolite Nomenclature). Examples ofintermediate pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22,silicalite 1, and silicalite 2. A small pore size zeolite has a poresize from about 3 Å to less than about 5.0 Å and includes, for example,CHA, ERI, KFI, LEV, SOD, and LTA framework type zeolites (IUPACCommission of Zeolite Nomenclature). Examples of small pore zeolitesinclude ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5,ZK-20, zeolite A, chabazite, zeolite T, and ALPO-17.

Many zeolites are synthesized in the presence of an organic directingagent, such as an organic nitrogen compound. For example, ZSM-5 may besynthesized in the presence of tetrapropylammonium cations and zeoliteMCM-22 may be synthesized in the presence of hexamethyleneimine. It isalso known to synthesize zeolites and related molecular sieves in thepresence of diquaternary directing agents. For example, U.S. Pat. No.5,192,521 discloses the synthesis of ZSM-12 in the presence ofbis(methylpyrrolidinium)-diquat-n cations, where n=4, 5 or 6.

According to the present invention, a new zeolite structure, designatedEMM-23 and having a unique X-ray diffraction pattern, has now beensynthesized using bis(N-propylpyrrolidinium)-diquat-n cations, where nis 5 or 6, as a structure directing agent.

SUMMARY

In one aspect, the invention resides in a molecular sieve materialhaving, in its as-calcined form, an X-ray diffraction pattern includingthe following peaks in Table 1:

TABLE 1 d-spacing (Å) Relative Intensity [100 × I/I(o)] 17.5-16.3 60-10010.6-10.1 5-50 9.99-9.56 20-70  6.23-6.06 1-10 5.84-5.69 1-10 5.54-5.401-10 4.29-4.21 1-10 3.932-3.864 1-10 3.766-3.704 5-40 3.735-3.674 1-103.657-3.598 1-10 3.595-3.539 1-20

Conveniently, the molecular sieve material has a composition comprisingthe molar relationship:X₂O₃:(n)YO₂,wherein n is at least about 10, X is a trivalent element, such as one ormore of B, Al, Fe, and Ga, especially Al, and Y is a tetravalentelement, such as one or more of Si, Ge, Sn, Ti, and Zr, especially Si.

In another aspect, the invention resides in a molecular sieve materialhaving, in its as-synthesized form, an X-ray diffraction patternincluding the following peaks in Table 2:

TABLE 2 d-spacing (Å) Relative Intensity [100 × I/I(o)] 17.6-16.3 60-10011.0-10.5 5-40 10.04-9.60  20-70  4.51-4.42 1-20 4.32-4.24 1-204.11-4.04 1-20 3.958-3.889 5-40 3.805-3.742 20-70  3.766-3.705 5-403.635-3.577 1-20 3.498-3.445 1-20 3.299-3.252 1-20

Conveniently, the molecular sieve material has a composition comprisingthe molar relationship:kF:mQ:X₂O₃:(n)YO₂,wherein 0≦k≦0.2, 0<m≦0.2, n is at least about 10, F is a source offluoride ion, such as one or more of F, HF, NH₄F, and NH₄HF₂, Q is anorganic structure directing agent, X is a trivalent element, such as oneor more of B, Al, Fe, and Ga, especially Al and Y is a tetravalentelement, such as one or more of Si, Ge, Sn, Ti, and Zr, especially Si.

Conveniently, Q comprises 1,5-bis(N-propylpyrrolidinium)pentanedications and/or 1,6-bis(N-propylpyrrolidinium)hexane dications.

In a further aspect, the invention resides in a process for producingthe molecular sieve material described herein, the process comprisingthe steps of:

(i) preparing a synthesis mixture capable of forming said material, saidmixture comprising water, a source of hydroxyl ions, a source of anoxide of a tetravalent element Y, optionally a source of a trivalentelement X, optionally a source of fluoride ions (F), and a directingagent (Q) comprising 1,5-bis(N-propylpyrrolidinium)pentane dicationsand/or 1,6-bis(N-propylpyrrolidinium)hexane dications, and said mixturehaving a composition, in terms of mole ratios, within the followingranges:

YO₂/X₂O₃ at least 10;

H₂O/YO₂ about 0.5 to about 30;

OH⁻/YO₂ about 0.1 to about 1.0;

F/YO₂ about 0.0 to about 0.25; and

Q/YO₂ about 0.05 to about 0.5;

(ii) heating said mixture under crystallization conditions including atemperature of from about 100° C. to about 200° C. and a time from about1 to about 14 days until crystals of said material are formed; and

(iii) recovering said crystalline material from step (ii).

In one embodiment, said mixture has a composition, in terms of moleratios, within the following ranges:

YO₂/X₂O₃ at least 100;

H₂O/YO₂ about 2 to about 10;

OH⁻/YO₂ about 0.2 to about 0.5;

F/YO₂ about 0.0; and

Q/YO₂ about 0.1 to about 0.25.

In yet a further aspect, the invention resides in a process forconverting a feedstock comprising an organic compound to a conversionproduct which comprises the step of contacting said feedstock with acatalyst at organic compound conversion conditions, said catalystcomprising an active form of the molecular sieve material describedherein.

In still yet a further aspect, the invention resides in an organicnitrogen compound comprising a dication having one of the followingstructures:

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 (a) and (b) show the X-ray diffraction patterns of theas-synthesized and calcined zeolites, respectively, of Example 4.

FIGS. 2 (a) to (d) are scanning electron micrograph (SEM) images of theproduct of Example 4 at different magnifications.

FIGS. 3 (a) and (b) are adsorption uptake curves showing, respectively,the adsorption of 2,2-dimethylbutane and 2,3-dimethylbutane at 120° C.by the calcined product of Example 5.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Described herein is a novel molecular sieve material, which isdesignated EMM-23, its synthesis in the presence of a structuredirecting agent comprising one or more novel diquaternary ammoniumcompounds and its use as an adsorbent and a catalyst for organicconversion reactions.

In particular, the novel molecular sieve structure EMM-23 ischaracterized by an X-ray diffraction pattern which, in the calcinedform of the molecular sieve, includes at least the peaks set out inTable 1 below and which, in the as-synthesized form of the molecularsieve, includes at least the peaks set out in Table 2 below.

TABLE 1 d-spacing (Å) Relative Intensity [100 × I/I(o)] 17.5-16.3 60-10010.6-10.1 5-50 9.99-9.56 20-70  6.23-6.06 1-10 5.84-5.69 1-10 5.54-5.401-10 4.29-4.21 1-10 3.932-3.864 1-10 3.766-3.704 5-40 3.735-3.674 1-103.595-3.539 1-20

TABLE 2 d-spacing (Å) Relative Intensity [100 × I/I(o)] 17.6-16.3 60-10011.0-10.5 5-40 10.04-9.60  20-70  4.51-4.42 1-20 4.32-4.24 1-204.11-4.04 1-20 3.958-3.889 5-40 3.805-3.742 20-70  3.766-3.705 5-403.635-3.577 1-20 3.498-3.445 1-20 3.299-3.252 1-20

The X-ray diffraction data reported herein were collected with aPANalytical X-Pert Pro diffraction system, equipped with a X′Celeratordetector, using copper K-alpha radiation. The diffraction data wererecorded by step-scanning at 0.017 degrees of two-theta, where theta isthe Bragg angle, and a counting time of 21 seconds for each step. Theinterplanar spacings, d-spacings, were calculated in Angstrom units, andthe relative peak area intensities of the lines, I/I(o), isone-hundredth of the intensity of the strongest line, above background,were determined with the MDI Jade peak profile fitting algorithm. Theintensities are uncorrected for Lorentz and polarization effects. Itshould be understood that diffraction data listed for this sample assingle lines may consist of multiple overlapping lines which undercertain conditions, such as differences in crystallographic changes, mayappear as resolved or partially resolved lines. Typically,crystallographic changes can include minor changes in unit cellparameters and/or a change in crystal symmetry, without a change in thestructure. These minor effects, including changes in relativeintensities, can also occur as a result of differences in cationcontent, framework composition, nature and degree of pore filling,crystal size and shape, preferred orientation and thermal and/orhydrothermal history.

In its calcined form, molecular sieve EMM-23 has a chemical compositioncomprising the molar relationship:X₂O₃:(n)YO₂,wherein n is at least about 10, typically greater than about 20, X is atrivalent element, such as one or more of B, Al, Fe, and Ga, especiallyAl, and Y is a tetravalent element, such as one or more of Si, Ge, Sn,Ti, and Zr, especially Si. It will be appreciated from the permittedvalues for n that EMM-23 can be synthesized in totally siliceous form inwhich the trivalent element X is absent or essentially absent.

In its as-synthesized and anhydrous form, molecular sieve EMM-23 has achemical composition comprising the molar relationship:kF:mQ:X₂O₃:(n)YO₂,wherein 0≦k≦0.2, 0<m≦0.2, n is at least about 10, typically greater thanabout 20, F is a source of fluoride, Q is an organic structure directingagent, X is a trivalent element, such as one or more of B, Al, Fe, andGa, especially Al and Y is a tetravalent element, such as one or more ofSi, Ge, Sn, Ti, and Zr, especially Si.

Conveniently, Q comprises 1,5-bis(N-propylpyrrolidinium)pentanedications and/or 1,6-bis(N-propylpyrrolidinium)hexane dications.

The Q and F components, which are associated with the as-synthesizedmaterial as a result of their presence during crystallization, areeasily removed by conventional post-crystallization methods.

The molecular sieve EMM-23 is thermally stable and in the calcined formexhibits a high surface area and significant hydrocarbon sorptioncapacity.

EMM-23 can be prepared from a synthesis mixture comprising sources ofwater, hydroxyl ions, an oxide of a tetravalent element Y, optionally atrivalent element X, optionally a source of fluoride (F) ions, and thestructure directing agent (Q) described above, the mixture having acomposition, in terms of mole ratios of oxides, within the followingranges:

Reactants Useful Preferred YO₂/X₂O₃ at least 10 at least 100 H₂O/YO₂0.5-30  2-10 OH⁻/YO₂ 0.1-1.0 0.2-0.5  F/YO₂   0-0.25 0 Q/YO₂ 0.05-0.5 0.1-0.25

Suitable sources of the tetravalent element Y depend on the element Yselected; but in the preferred embodiments, in which Y is silicon and/orgermanium, include colloidal suspensions of silica, precipitated silica,fumed silica, alkali metal silicates, tetraalkyl orthosilicates andgermanium oxide. If present, the trivalent element X is normallyaluminum and suitable sources of aluminum include hydrated alumina,aluminum hydroxide, alkali metal aluminates, aluminum alkoxides, andwater-soluble aluminum salts, such as aluminum nitrate. If present,suitable sources of fluoride ions include one or more of F, HF, NH₄F,and NH₄HF₂.

Suitable sources of Q are the hydroxides and/or salts of the relevantdiquaternary ammonium compounds. Although the compounds themselves arebelieved to be novel, they can readily be synthesized by reaction ofN-propylpyrrolidine with 1,5-dibromopentane or 1,6-dibromohexane.

The reagents are typically mixed together by a mechanical process suchas stirring or high shear blending to assure suitable homogenization ofthe synthesis mixture. Depending on the nature of the reagents it may benecessary to reduce the amount of water in the mixture beforecrystallization to obtain the preferred H₂O/YO₂ molar ratio. Suitablemethods for reducing the water content are evaporation under a static orflowing atmosphere such as ambient air, dry nitrogen, dry air, or byspray drying or freeze drying.

Crystallization of EMM-23 can be carried out at either static or stirredconditions in a suitable reactor vessel, such as for example,polypropylene jars or teflon lined or stainless steel autoclaves, at atemperature of about 100° C. to about 200° C. for a time sufficient forcrystallization to occur at the temperature used, e.g., from about 1 dayto about 14 days. Thereafter, the crystals are separated from the liquidand recovered.

To the extent desired and depending on the X₂O₃/YO₂ molar ratio of thematerial, any cations in the as-synthesized EMM-23 can be replaced inaccordance with techniques well known in the art by ion exchange withother cations. Preferred replacing cations include metal ions, hydrogenions, hydrogen precursor, e.g., ammonium ions and mixtures thereof.Particularly preferred cations are those which tailor the catalyticactivity for certain hydrocarbon conversion reactions. These includehydrogen, rare earth metals and metals of Groups 2 to 15 of the PeriodicTable of the Elements. As used herein, the numbering scheme for thePeriodic Table Groups is as disclosed in Chemical and Engineering News,63(5), 27 (1985).

The molecular sieve described herein may be subjected to treatment toremove part or all of the organic directing agent Q used in itssynthesis. This is conveniently effected by thermal treatment in whichthe as-synthesized material is heated at a temperature of at least about370° C. for at least 1 minute and generally not longer than 20 hours.While subatmospheric pressure can be employed for the thermal treatment,atmospheric pressure is desired for reasons of convenience. The thermaltreatment can be performed at a temperature up to about 925° C. Thethermally-treated product, especially in its metal, hydrogen andammonium forms, is particularly useful in the catalysis of certainorganic, e.g., hydrocarbon, conversion reactions.

The present molecular sieve may be intimately combined with ahydrogenating component, such as molybdenum, tungsten, rhenium, nickel,cobalt, chromium, manganese, or a noble metal such as platinum orpalladium where a hydrogenation-dehydrogenation function is to beperformed. Such component can be in the composition by way ofcocrystallization, exchanged into the composition to the extent a GroupIIIA element, e.g., aluminum, is in the structure, impregnated thereinor intimately physically admixed therewith. Such component can beimpregnated in or on to it such as, for example, by, in the case ofplatinum, treating the silicate with a solution containing a platinummetal-containing ion. Thus, suitable platinum compounds for this purposeinclude chloroplatinic acid, platinous chloride and various compoundscontaining the platinum amine complex.

The present molecular sieve, when employed either as an adsorbent or asa catalyst should be dehydrated, at least partially. This can be done byheating to a temperature in the range of 200° C. to about 370° C. in anatmosphere such as air, nitrogen, etc., and at atmospheric,subatmospheric or superatmospheric pressures for between 30 minutes and48 hours. Dehydration can also be performed at room temperature merelyby placing the EMM-23 in a vacuum, but a longer time is required toobtain a sufficient amount of dehydration.

The present molecular sieve can be used as an adsorbent or, particularlyin its aluminosilicate form, as a catalyst to catalyze a wide variety oforganic compound conversion processes including many of presentcommercial/industrial importance. Examples of chemical conversionprocesses which are effectively catalyzed by the crystalline material ofthis invention, by itself or in combination with one or more othercatalytically active substances including other crystalline catalysts,include those requiring a catalyst with acid activity. Examples oforganic conversion processes which may be catalyzed by EMM-23 includecracking, hydrocracking, disproportionation, alkylation,oligomerization, and isomerization.

As in the case of many catalysts, it may be desirable to incorporateEMM-23 with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring, or in the form of gelatinous precipitates or gels, includingmixtures of silica and metal oxides. Use of a material in conjunctionwith EMM-23, i.e., combined therewith or present during synthesis of thenew crystal, which is active, tends to change the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtained in aneconomic and orderly manner without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. Said materials, i.e., clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These clayand/or oxide binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with EMM-23 includethe montmorillonite and kaolin family, which families include thesubbentonites, and the kaolins commonly known as Dixie, McNamee, Georgiaand Florida clays or others in which the main mineral constituent ishalloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can beused in the raw state as originally mined or initially subjected tocalcination, acid treatment or chemical modification. Binders useful forcompositing with EMM-23 also include inorganic oxides, such as silica,zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.

In addition to the foregoing materials, EMM-23 can be composited with aporous matrix material such as silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia, silica-titania as wellas ternary compositions such as silica-alumina-thoria,silica-alumina-zirconia silica-alumina-magnesia andsilica-magnesia-zirconia.

The relative proportions of EMM-23 and inorganic oxide matrix may varywidely, with the EMM-23 content ranging from about 1 to about 90 percentby weight, and more usually, particularly when the composite is preparedin the form of beads, in the range of about 2 to about 80 weight percentof the composite.

The invention will now be more particularly described with reference tothe following non-limiting Examples and the accompanying drawings.

Example 1

A synthesis gel with molar ratios of H₂O/SiO₂=4, Si/Al=50, andOH⁻/SiO₂=0.5 was prepared according to the following procedure.

Alumina trihydrate, 0.016 g, was thoroughly mixed with 4.17 g of anaqueous hydroxide solution of 1,5-bis(N-propylpyrrolidinium)pentane([OH⁻]=1.20 mmol/g) within a tared Teflon liner.Tetramethylorthosilicate (TMOS), 1.54 g, was then added to the mixture.The open liner was then placed in a vented hood in order to allow themethanol and water to evaporate. After 3 days, extra water was added tobring the H₂O/SiO₂ molar ratio to 4 (as determined by the total mass ofthe suspension). The liner was then capped and sealed within an 23 mLsteel Parr autoclave. The autoclave was placed on a spit within aconvection oven at 150° C. The autoclave was tumbled at 50 rpm over thecourse of 10 days inside the heated oven. The autoclave was then removedand allowed to cool to room temperature. The solids were then recoveredby filtration and washed thoroughly with deionized water (>250 mL) andthen acetone (about 20 mL). The solids were allowed to dry in an oven at100° C. for 2 hours. The resulting product was analyzed by powder XRDand shown to be EMM-23 with minor amount of zeolite beta.

Example 2

A synthesis gel with molar ratios of H₂O/(SiO₂+GeO₂)=4, Si/Ge=7.3, andOH⁻/SiO₂=0.5 was prepared according to the following procedure.

Germanium oxide, 0.13 g, was thoroughly mixed with 4.17 g of an aqueoushydroxide solution of 1,5-bis(N-propylpyrrolidinium)pentane ([OH⁻]=1.20mmol/g) within a tared Teflon liner. TMOS, 1.36 g, was then added to themixture. The open liner was then placed in a vented hood in order toallow the methanol and water to evaporate. After 3 days, extra water wasadded to bring the H₂O/(SiO₂+GeO₂) molar ratio to 4 (as determined bythe total mass of the suspension). The liner was then capped and sealedwithin an 23 mL steel Parr autoclave. The autoclave was placed on a spitwithin a convection oven at 150° C. The autoclave was tumbled at 50 rpmover the course of 10 days inside the heated oven. The product wasworked up according to the procedure in Example 1. Powder XRD showed theproduct to be a mixture of EMM-23 and ITQ-17.

Example 3

A synthesis gel with molar ratios of H₂O/SiO₂=5 and OH⁻/SiO₂=0.5 wasprepared according to the following procedure.

An aqueous hydroxide solution of 1,5-bis(N-propylpyrrolidinium)pentane,4.17 g, ([OH]=1.20 mmol/g) were mixed with 1.54 g TMOS within a taredTeflon liner. Seeds, 0.02 g of the product from Example 1, were added tothe gel. Two small steel balls (about 4 mm in diameter) were next addedto the synthesis gel. The open liner was then placed in a vented hood inorder to allow the methanol and water to evaporate. After 3 days, extrawater was added to bring the H₂O/SiO₂ ratio to 5 (as determined by thetotal mass of the suspension). The liner was then capped and sealedwithin an 23 mL steel Parr autoclave. The autoclave was placed on a spitwithin a convection oven at 150° C. The autoclave was tumbled at 50 rpmover the course of 6 days inside the heated oven. The product was workedup according to the procedure in Example 1. Powder XRD showed theproduct to be a mixture of EMM-23 and amorphous material.

Example 4

A synthesis gel with molar ratios of H₂O/SiO₂=5, Si/Al=75, andOH⁻/SiO₂=0.5 was prepared according to the following example.

Alumina trihydrate, 0.013 g, was thoroughly mixed with 4.71 g of anaqueous hydroxide solution of 1,5-bis(N-propylpyrrolidinium)pentane([OH⁻]=1.20 mmol/g) within a tared Teflon liner. TMOS, 1.74 g, was thenadded to the mixture. Seeds, 0.02 g of the product from Example 1, wereadded to the gel. Two small steel balls (about 4 mm in diameter) werenext added to the synthesis gel. The open liner was then placed in avented hood in order to allow the methanol and water to evaporate. After2 days, extra water was added to bring the H₂O/SiO₂ molar ratio to 5 (asdetermined by the total mass of the suspension). The liner was thencapped and sealed within an 23 mL steel Parr autoclave. The autoclavewas placed on a spit within a convection oven at 150° C. The autoclavewas tumbled at 50 rpm over the course of 6 days inside the heated oven.The product was worked up according to the procedure in Example 1. Thelines of the X-ray diffraction pattern of the as-synthesized product aregiven in Table 3. The A % is the intensity of the peak relative to themost intense peak in the pattern.

TABLE 3 2-Theta (degrees) d(Å) A % 5.22 16.903 100 8.25 10.706 19.7 9.009.818 38 12.77 6.926 3.5 13.73 6.446 4.4 15.13 5.853 2.4 15.58 5.682 1.416.46 5.382 1.9 17.97 4.933 1.7 18.74 4.731 2.6 19.86 4.467 6.6 20.144.405 4.3 20.75 4.277 7.7 21.80 4.074 6.9 22.07 4.024 2.4 22.65 3.923 1123.56 3.773 31.7 23.80 3.736 12 24.42 3.642 5.3 24.67 3.606 7 25.643.471 6.7 26.02 3.421 3.3 26.88 3.315 6 27.05 3.294 5.4 27.20 3.275 9.327.54 3.236 1.4 27.71 3.217 1.4 28.29 3.152 0.8 29.06 3.070 3.7 29.753.001 3.6 29.99 2.977 1.1 30.71 2.909 1.5 31.43 2.844 0.5 31.82 2.8102.3 32.49 2.754 4 33.75 2.654 1.5 34.33 2.610 0.6 35.04 2.559 2.1 35.902.499 0.3 36.70 2.447 1 36.95 2.431 0.5 37.35 2.406 1.4 37.84 2.376 0.638.09 2.361 0.5 38.35 2.345 0.4 38.58 2.332 0.6 39.04 2.305 0.5 39.602.274 0.7 40.07 2.248 0.7 40.38 2.232 0.4 41.18 2.190 0.4 41.79 2.1601.5 42.77 2.113 0.5 43.36 2.085 0.7 43.83 2.064 0.9 44.24 2.046 0.744.61 2.030 2.1 45.26 2.002 1.3 45.79 1.980 1.6 46.13 1.966 1.6 46.641.946 0.4 47.11 1.928 0.5 47.84 1.900 2.4 48.46 1.877 0.7 49.06 1.8551.1 49.72 1.832 1.1

A portion of the resultant product was calcined according to thefollowing procedure. The zeolite was heated inside a muffle furnace fromambient temperature to 400° C. at 4° C./min under a nitrogen atmosphere,then heated to 550° C. at 4° C./min in air, and maintained at 550° C. inair for 2 hours. FIGS. 1 (a) and (b) show the powder XRD patterns of theas-synthesized and calcined zeolites, respectively, and indicate thematerial to be pure EMM-23. The lines of the X-ray diffraction patternof the calcined product is given in Table 4.

TABLE 4 2-Theta (degrees) d(Å) A % 5.23 16.880 100 8.51 10.382 21.9 9.049.773 43.6 13.43 6.589 2.2 13.79 6.418 1.3 14.41 6.144 4.1 15.35 5.7692.6 15.65 5.660 1.7 16.20 5.469 3.8 17.02 5.205 1.5 18.83 4.708 0.419.29 4.598 1 20.02 4.431 0.5 20.67 4.293 2.5 20.91 4.246 3 21.97 4.0430.3 22.58 3.935 0.9 22.80 3.898 3.5 23.19 3.833 1.3 23.80 3.735 10.624.01 3.704 3.2 24.52 3.627 4.1 24.94 3.567 5.6 26.22 3.397 1.5 26.543.356 0.5 27.01 3.298 1 27.27 3.268 2.5 27.74 3.213 1.9 28.55 3.124 1.429.02 3.075 0.4 29.56 3.020 1.1 30.03 2.973 0.3 30.56 2.923 0.6 31.532.835 0.5 33.31 2.688 0.4 34.61 2.589 0.3

Scanning electron micrograph (SEM) images of the product of Example 4 atdifferent magnifications are shown in FIGS. 2 (a) to (d).

Example 5

Example 3 was repeated except that 0.02 g of seeds from Example 4 wereused instead of seeds from Example 1. The product was worked up after 4days of heating at 150° C. Powder XRD showed the product to be pureEMM-23.

Example 6

Example 5 was repeated except the heating period was extended to 7 days.Powder XRD showed the product to be pure EMM-23.

Example 7

Example 4 was repeated with Si/Al=50 and with 0.02 g seeds from Example4 being used instead of seeds from Example 1. The product was worked upafter 6 days of heating at 150° C. Powder XRD showed the product to bepure EMM-23.

Example 8

An as-made sample from Example 4 was placed within a tube furnacesupplied with dry air flow through an ozone generator. The sample wasfirst heated to 150° C. in the presence of flowing air (3500 mL/min),and then the ozone generator was then switched on to give 1-1.2% ozoneto the tube furnace. After heating the sample at 150° C. for a total of5 hours in the presence of ozone, the ozone generator was switched offand the reactor was allowed to cool to ambient temperatures. Powder XRDindicates that the sample remains crystalline after this treatment(Table 3 shows the characteristic peaks) but that the peak positions andintensities are different from those of the sample calcined to 550° C.Thermogravimetric analysis and mass spectrometry (TGA/MS) indicate thatthe sample contains no carbonaceous material after the treatment withozone. A portion of the sample was dried under vacuum at 300° C. andflame sealed in a 1 mm quartz capillary. Table 5 gives the XRD patterntaken using synchrotron radiation at λ=0.8668 and a 2-theta stepsize=0.005 degrees.

TABLE 5 2-Theta (degrees) d(Å) A % 2.92 17.001 100 4.65 10.675 37.1 5.069.815 47.4 5.85 8.498 1.5 7.25 6.858 2.4 7.74 6.425 3.2 7.82 6.359 58.54 5.818 4.3 8.78 5.665 4.5 8.85 5.620 4.9 9.32 5.336 1.7 10.55 4.7140.8 10.61 4.689 1.2 11.15 4.460 0.2 11.27 4.415 1.7 11.39 4.368 4.111.71 4.250 4 12.26 4.060 0.8 12.36 4.026 2.9 12.47 3.991 1.7 12.763.900 2.9 12.81 3.885 2.1 13.27 3.751 18.6 13.36 3.725 8.7 13.42 3.7106.2 13.78 3.612 3.5 13.90 3.581 5.7 13.99 3.558 0.9 14.52 3.429 3.614.65 3.400 2.8 15.17 3.283 4 15.22 3.272 4 15.39 3.238 7.6 15.50 3.2130.9 15.66 3.181 1.3 15.93 3.129 0.6 16.36 3.047 3.6 16.48 3.025 0.316.72 2.981 1.4 16.80 2.967 2.1 16.88 2.953 0.8 16.99 2.934 0.3 17.302.881 1.7 17.85 2.794 0.8 17.98 2.774 0.8 18.28 2.728 2.5 18.33 2.7210.2 18.42 2.708 0.2 18.98 2.629 1.1 19.25 2.592 0.5 19.64 2.542 0.519.78 2.523 0.9 20.21 2.470 0.3 20.56 2.429 0.8 20.73 2.409 0.9 20.932.386 0.6 21.06 2.372 0.3 21.18 2.358 0.4 21.35 2.340 0.7 21.67 2.3060.2 21.84 2.288 0.3 22.16 2.255 0.2 22.43 2.229 0.4 22.65 2.207 0.323.35 2.142 0.9 23.87 2.095 0.2 23.98 2.086 0.2 24.19 2.069 0.3 24.342.056 0.2 24.48 2.044 0.4 24.65 2.030 0.4 24.78 2.020 0.2 25.26 1.9820.5 25.41 1.971 0.8 25.50 1.964 0.5 25.57 1.959 0.4 25.67 1.951 0.825.75 1.945 0.6 25.96 1.930 0.5 26.19 1.913 0.8 26.47 1.893 0.4 26.611.883 0.6 26.74 1.875 1.2 27.06 1.853 0.6 27.21 1.843 0.5 27.28 1.8380.3 27.60 1.817 0.3 27.73 1.809 0.4 28.14 1.783 0.6 28.39 1.767 0.528.70 1.749 0.2 28.83 1.741 0.4 29.21 1.719 0.8 29.58 1.698 0.5 29.731.690 0.5 30.01 1.674 1 30.28 1.659 0.5

Examples 9 to 19

A series of small scale syntheses were run within the 1.5 cc wells of aparallel synthesis reactor. Each of the syntheses used a new stainlesssteel liner with a steel ball. In each Example, TMOS was the source ofsilica. Where present, germanium oxide was the source of germanium, andaluminum nitrate was the source of aluminum. In Examples 9 to 15, thestructure directing agent was 1,5-bis(N-propylpyrrolidinium)pentanedihydroxide, whereas in Examples 16 to 19 the structure directing agentwas 1,6-bis(N-propylpyrrolidinium)hexane dihydroxide. The composition ofeach of the synthesis mixtures (in molar ratios) is summarized in Table7 below.

TABLE 7 SDA(OH)₂/ Example H₂O/(Si + Ge) Si/Ge Si/Al HF/(Si + Ge) (Si +Ge) Syntheses with 1,5-bis(N-propylpyrrolidinium)pentane dihydroxide 9 44 — 0 0.25 10 4 7.3 — 0 0.25 11 4 — — 0.125 0.25 12 4 — 100 0 0.25 13 4— 100 0.125 0.25 14 4 — — 0 0.25 15 10 — 100 0.125 0.25 Syntheses with1,6-bis(N-propylpyrrolidinium)hexane dihydroxide 16 4 4 — 0 0.25 17 47.3 — 0 0.25 18 4 — 100 0 0.25 19 4 — 100 0.125 0.25

After addition of the reactants, the reaction mixtures were freeze-driedto remove most of the water and methanol and then water was added toadjust the H₂O/SiO₂ molar ratio to the designated level. The reactor wasrotated in rotisserie oven at 150° C. for 10 days. The products wereworked up by 2 iterations of centrifugation and washings with deionizedwater and in each case the product was pure EMM-23.

Example 20

The calcined product of Example 5 was tested for its capacity to adsorbn-hexane at 90° C., 2,2-dimethylbutane and 2,3-dimethylbutane at 120° C.and the results are summarized below:

-   -   n-hexane—120 mg/g    -   2,2-dimethylbutane—73 mg/g    -   2,3-dimethylbutane—75 mg/g

Adsorption uptake curves showing the adsorption of 2,2-dimethylbutaneand 2,3-dimethylbutane at 120° C. by the product of Example 5 are shownin FIGS. 3 (a) and (b), respectively.

The adsorption data suggest that EMM-23 is a molecular sieve includingpores defined by 12-membered ring of tetrahedrally coordinated atoms.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

The invention claimed is:
 1. A molecular sieve material having, in itsas-calcined form, an X-ray diffraction pattern including the followingpeaks in Table 1: TABLE 1 d-spacing (Å) Relative Intensity [100 ×I/I(o)] 17.5-16.3 60-100 10.6-10.1 5-50 9.99-9.56 20-70  6.23-6.06 1-105.84-5.69 1-10 5.54-5.40 1-10 4.29-4.21 1-10 3.932-3.864 1-103.766-3.704 5-40 3.735-3.674 1-10 3.657-3.598 1-10 3.595-3.539  1-20.


2. The material of claim 1, and having a composition comprising themolar relationshipX₂O₃:(n)YO₂, wherein n is at least about 10, X is a trivalent element,and Y is a tetravalent element.
 3. The material of claim 2, wherein Xincludes one or more of B, Al, Fe, and Ga, and Y includes one or more ofSi, Ge, Sn, Ti, and Zr.
 4. The material of claim 2, wherein X includesaluminum, and Y includes silicon and/or germanium.
 5. The molecularsieve material of claim 1 having, in its as-synthesized form, an X-raydiffraction pattern including the following peaks in Table 2: TABLE 2d-spacing (Å) Relative Intensity [100 × I/I(o)] 17.6-16.3 60-10011.0-10.5 5-40 10.04-9.60  20-70  4.51.4.42 1-20 4.32-4.24 1-204.11-4.04 1-20 3.958-3.889 5-40 3.805-3.742 20-70  3.766-3.705 5-403.635-3.577 1-20 3.498-3.445 1-20 3.299-3.252  1-20.


6. The material of claim 5, and having a composition comprising themolar relationship:kF:mQ:X₂O₃:(n)YO₂, wherein 0≦k≦0.2, 0<m≦0.2, n is at least about 10, Fis a source of fluoride, Q is an organic structure directing agent, X isa trivalent element, and Y is a tetravalent element.
 7. The material ofclaim 6, wherein X includes aluminum, and Y includes silicon.
 8. Thematerial of claim 6, wherein X includes one or more of B, Al, Fe, or Ga,and Y includes one or more of Si, Ge, Sn, Ti, or Zr.
 9. The material ofclaim 6, wherein F includes one or more of F, HF, NH₄F, and NH₄HF₂. 10.The material of claim 6, wherein Q comprises1,5-bis(N-propylpyrrolidinium)pentane dications and/or1,6-bis(N-propylpyrrolidinium)hexane dications.
 11. A process forproducing said molecular sieve material of claim 6, the processcomprising the steps of: (i) preparing a synthesis mixture capable offorming said crystalline molecular sieve material, said mixturecomprising water, a source of hydroxyl ions, a source of an oxide of atetravalent element Y, a source of a trivalent element X, optionally asource of fluoride ions, and a directing agent (Q) comprising1,5-bis(N-propylpyrrolidinium)pentane dications and/or1,6-bis(N-propylpyrrolidinium)hexane dications, and said mixture havinga composition, in terms of mole ratios, within the following ranges:YO₂/X₂O₃ at least 10; H₂O/YO₂ about 0.5 to about 30; OH⁻/YO₂ about 0.1to about 1.0; F/YO₂ about 0.0 to about 0.25; and Q/YO₂ about 0.05 toabout 0.5; (ii) heating said mixture under crystallization conditionsincluding a temperature of from about 100° C. to about 200° C. and atime from about 1 to about 14 days until crystals of said molecularsieve material are formed; and (iii) recovering said crystals of saidmolecular sieve material from step (ii) wherein said molecular sievematerial having, in its as-synthesized form, said X-ray diffractionpattern including the peaks shown in Table 2, and in its as-calcinedform, said X-ray diffraction pattern including the following peaks inTable
 1. 12. The process of claim 11 where said mixture having acomposition, in terms of mole ratios, within the following ranges:YO₂/X₂O₃ at least 100; H₂O/YO₂ about 2 to about 10; OH⁻/YO₂ about 0.2 toabout 0.5; F/YO₂ about 0.0; and Q/YO₂ about 0.1 to about 0.25.
 13. Amolecular sieve material produced by the process of claim 11, whereinsaid molecular sieve material having, in its as-synthesized form, saidX-ray diffraction pattern including the peaks shown in Table 2, and inits as-calcined form, said X-ray diffraction pattern including thefollowing peaks in Table
 1. 14. A process for converting a feedstockcomprising an organic compound to a conversion product which comprisesthe step of contacting said feedstock with a catalyst, at organiccompound conversion conditions, said catalyst comprising an active formof said molecular sieve material of claim 1, wherein said molecularsieve material having, in its as-calcined form, said X-ray diffractionpattern including the following peaks in Table 1.